Stable Mineral Research Articles

Synthesis of Electrolytic Manganese Slag-Solid Waste-Based Geopolymers: Compressive Strength and Mn Immobilization.

The massive stockpiling of electrolytic manganese residue (EMR) has caused serious environmental pollution. In this study, EMR, coal gangue (CG), and fly ash (FA) were used as raw materials to obtain the optimal mix ratio based on Design-Expert mixture design. The effects of activator modulus, liquid-solid (L/S) ratio, and curing temperature on the mechanical properties of geopolymers were investigated. The results showed that the compressive strength of the prepared geopolymer was 12.0 MPa, and the 28d leaching of Mn was 0.123 mg/L under the conditions of EMR:CG:FA = 0.43:0.34:0.23, L/S = 0.9, a curing temperature of 60 °C, and a curing time of 24 h. This indicates that the geopolymer is an environmentally friendly material with high compressive strength. The mineral composition of the geopolymer is mainly hydrated calcium silicate and geopolymer gel. In addition, a more stable new mineral phase, MnSiO3, was generated. The Fourier transform infrared (FTIR) spectrogram showed that the peak at 1100 m-1 was shifted to 1112 cm-1, which indicated that a geopolymerization reaction had occurred. Through scanning electron microscopy (SEM) and energy dispersive spectrum (EDS) analysis, it was identified that the geopolymerization produced a large amount of amorphous gelatinous substances with a relatively dense structure, the major elements being oxygen, silicon, aluminum, calcium, and sodium.

Geochemistry of hydrothermal and stream sedimentary rutile in the Tiegelongnan porphyry-epithermal Cu (Au) deposit, Tibet: A tool for exploration

Rutile is a common and stable mineral in porphyry Cu deposits, and morphology and geochemistry of rutile are recognized as a potential indicator mineral for exploration. In this study, we investigate physical features and chemical composition of hydrothermal rutile in the Tiegelongnan porphyry-epithermal system, as well as rutile in stream sediments nearby to establish a method to apply rutile as an exploration proxy. Four stages of hydrothermal rutile have been identified. Potassic alteration stage rutile (Rt1) is associated with biotite, with elongated and acicular shape and small grain size (20–50 μm). Rutile from lower temperature phyllic alteration (Rt2), quartz veins (Rt3), and advanced argillic alteration (Rt4), has characteristic sector zoning and larger grain size (50–150 μm). The sector zoning is more commonly present in Rt2, Rt3, Rt4, that are associated with high-grade Cu mineralization, and is associated with incorporation of W, Fe, V, Sn, and Zr. The earlier rutile (Rt1) also has a geochemical signature different from the other three types of rutile, characterized by significantly lower Al, Cu, Zr, Nb, Sn, Hf, and higher Sc and Fe contents. Low-temperature hydrothermal alteration stage rutile (Rt2, 3, 4) share many geochemical similarities, but Rt3 has higher Nb and Ta contents (median = 3371.0 and 176.0 ppm, respectively), whereas Rt4 has higher Sb content (median = 24.3 ppm).Rutile trace element data from this study and literature are integrated to develop a Partial Least Square-Discriminant Analysis (PLS-DA) multivariate statistics plots that can discriminate porphyry Cu deposit rutile from orogenic gold and VHMS deposits, as well as rutile from different alteration stages. The PLS-DA plots predict that stream sedimentary gold-bearing rutile (RtSAu) adjacent to the Tiegelongnan deposit are derived from the deposit, and mainly from low-temperature phyllic and advanced argillic alteration stages. This is consistent with geochemical similarity between the RtSAu and the Tiegelongnan low-temperature hydrothermal rutile (Rt2 + Rt4). This is further confirmed by a U-Pb age of 125.3 ± 4.7 Ma (n = 24, 2σ) for RtSAu, which is consistent with the main porphyry mineralization age of ∼ 120 Ma in the Tiegelongnan deposit. We infer that the RtSAu may have formed during the ∼120 Ma epithermal system at Tiegelongnan, which has already largely eroded. In general, our findings prove the capability of using rutile, by combing the texture, geochemical compositions, geochronology, PLS-DA tools, and their spatial distribution, as a proxy mineral for the exploration of porphyry Cu deposits.

Relationship of lithological data with the sedimentation environment of the Upper Batian deposits of the Kogalym region

Research subject. Upper Batian deposits (formation U2) of the Eastern part of the Kogalym region, within the North Nizhnevartovsk monocline. Aim. Reconstruction of the sedimentation environment of the U2 formation in the Kogalym region. Materials and methods. The reconstruction of sedimentation environments was conducted based on a macroscopic description of core samples with identification of structural and textural features of rocks from 35 wells. The clarification of sedimentation settings was carried out based on the description of 41 thin sections and a granulometric analysis of the clastic part of the studied rocks. Results. According to the macroscopic study, the U2 layer is composed of an uneven alternation of silty-argillaceous and silty-sandy rocks with coal interlayers. The rocks are of a polyfacial nature, represented by deposits of continental, transitional, and marine genesis. The thickness of the deposits varies markedly depending on the paleorelief of the area. The optical petrographic study revealed the polymictic composition of the studied rocks, which, according to the classification by V.D. Shutova, correspond to the arkose (graywacke arkose), less often graywacke (feldspar-quartz, quartz-feldspar greywackes) group. Cement most often exhibits a carbonate-clay composition. Rocks of marine genesis are characterized by a decrease in the proportion of rock fragments and an increase in the proportion of mechanically stable accessory minerals (zircon, garnet, tourmaline). The rocks of continental genesis are characterized by the maximum content of micas and plant detritus. An increase in the content of pyrite is noted in the sediments transitional from the continent to the sea. The grain-size analysis data of reservoir rocks of the U2 formation showed that both coastal-marine and channel deposits were formed in environments with active hydrodynamics of the medium, when the dynamic processing of clastic material exceeded the intensity of its supply. Conclusions. The performed lithofacies studies made it possible to reconstruct the sedimentation environment, as well as to reveal specific features in the distribution of the silty-sandy rock components of the U2 formation.

Aqueous alteration in icy planetesimals: The effect of outward transport of gaseous hydrogen

Parent bodies of carbonaceous chondrites that initially contained metallic iron potentially exert strong reduction power during aqueous alteration to generate molecular hydrogen in excess of hydrogen solubility in water-rich fluids. The surplus hydrogen escapes from the system, which is subsequently supplied to overlying regions in planetesimals. Based on this concept, we conducted chemical equilibrium modeling of the aqueous alteration and simulated gaseous H2 migration within the icy planetesimal that has a melted mantle and an icy shell during the early stages of radiogenic heating. In the chemical equilibrium modeling, we simulated the aqueous alteration of chondritic rocks at 0–350 °C and a water/rock mass ratio of 0.2–10 with initial CO2 contents of 0–10 mol% in the fluid. The results showed that the mineral assemblage and solution composition change with the temperature, water/rock mass ratio, and initial fluid composition. The reproduced mineral paragenesis and abundance well explain those of carbonaceous chondrites. Furthermore, it was revealed that the initial H2 fugacity of the system influences not only the stability of minerals and solution compositions, but also the preservation potential of organic molecules. Indeed, within these parameter spaces, the modeling results account for the organic/inorganic carbon-rich alterations reported for the Tagish Lake meteorite, Ceres, and Ryugu. Simulations of gaseous H2 migration in a planetesimal revealed that gaseous H2 in the deep interior can be transported to the interface with an icy shell even if the permeability is low. Moreover, it is highly possible that an H2-rich layer would have been widely formed just below the icy shell. Therefore, it is expected that H2-rich regions beneath the ice layer in planetesimals have substantial potential for the synthesis and preservation of organic molecules. These results imply that the alteration of carbonaceous chondrite parent bodies and C-complex asteroids is characterized by not only the type of parent bodies (e.g., formation age and distance from the Sun) but also the locations within their parent bodies.

Olivine-Hosted Melt Inclusions Track Progressive Dehydration Reactions in Subducting Slabs Across Volcanic Arcs

Abstract The stability and breakdown of mineral phases in subducting slabs control the cycling of trace elements through subduction zones. Stability of key minerals and the partitioning of trace elements between these minerals and liquid phases of interests have been charted by natural sample analysis and experimental constraints. However, systematic study from arc front to far back arc has rarely shown that the expected geochemical variations of the slab liquid are actually recorded by natural samples. Complexities arise by uncertainties on the nature of the slab component (melts, fluids and supercritical liquids), source heterogeneities and transport processes. Using data from olivine-hosted melt inclusions sampled along and across the NE Japan and southern Kurile arcs, we demonstrate that experimentally and thermodynamically constrained phase stabilities in subducted materials indeed control the trace element signatures as predicted by these models and experiments. The main reactions that can be traced across arc are progressive breakdown of light rare earth element-rich accessory phases (e.g. allanite), enhanced dehydration of the lithospheric mantle (serpentine breakdown) and changes in the nature of the slab component. This work elucidates subduction zone elemental cycling in a well-characterized petrogenetic setting and provides important constraints on the interpretation of trace element ratios in arc magmas in terms of the prograde metamorphic reactions within the subducting slab.

Influence of chlorine on co-processing of hazardous wastes in brick kilns

Brick kiln co-treatment is a novel industrial hazardous wastes (IHWs) utilization process. However, the effects of chlorine (Cl) in wastes on heavy metals (HMs) during this process are overlooked. This study investigated the stabilization/solidification (S/S) and volatilization, as well as long and short-term leaching, of HMs in Cl-containing bricks. The results indicated enhanced formations of stable mineral phases (NiFe2O4, Ni2SiO4, Cd3Al2Si3O12, CdSiO3, FeCr2O4, Cr2O3, CuFe2O4, and CuAl2O4) in bricks at a low sintering temperature (800 °C) due to the affinity between Cl and HMs. By comparing HM concentrations before and after sintering in bricks, the study observed that Cl's presence significantly elevated the volatilization rates for Cd and Cu by 30.8% and 14.2%, respectively. In contrast, the effect on volatilization for Ni and Cr was not significant. Additionally, utilizing the NEN 7375 method, the cumulative leaching rates of Ni, Cd, Cr, and Cu over a 64-day experiment under extremely acidic conditions were 0.22%, 7.18%, 0.01%, and 1.46%, respectively. Similarly, higher short-term leaching rates of Cd (4.03%) and Cu (5.73%) than those of Ni (0.94%) and Cr (0.08%) were observed. This finding might be attributed to the lower stability of the Cd and Cu solid phases under acidic environments compared to those of Ni and Cr. Surface wash-off, dissolution, and diffusion were the processes governing HM leaching from bricks. The 10-year projections revealed a minimal release of HMs during future extended leaching, implying the successful S/S of HMs. This study provides a reference for assessing the environmental impacts of brick kiln co-processing of Cl-containing IHWs.

Geochemical effects of carbonated water on reservoir and caprock minerals for carbon capture and storage

CO2 can be safely stored in geological formations, such as deep saline aquifers and depleted oil or gas reservoirs. However, knowledge about caprock and storing bed integrity is essential for safe storage in sedimentary porous rocks. In this study typical carbonate and sandstone minerals present in the reservoir and caprocks have been exposed to carbonated water above supercritical conditions of CO2 for short time periods (7 days) to investigate the CO2-brine-rock interactions and their effects on mineral stability. After exposure, the equilibrated brine composition was determined and any changes to the mineral samples were examined by SEM, EDX and XRD analyses. The solubility of CO2 in brines was low, increasing with pressure and decreasing with salinity, and no significant increase in CO2 solubility was observed above critical pressure and temperature for CO2. Quartz and clay minerals were the least reactive sandstone minerals, while ion exchange reactions were observed for the feldspar minerals. For calcite minerals, calcium ion liberation was observed accompanied by a pH increase, which is linked to mineral dissolution. SEM, EDX and XRD analyses did not detect any changes on the surfaces of silicate and carbonate minerals exposed to the carbonated water. The overall results confirm minimal effects on silicate and carbonate minerals after short-term exposure to carbonated water above supercritical conditions of CO2.

Pre-treatment through reductive calcination for CO2 mineralization and selective battery metal extraction from laterites

The world needs an increasing supply of nickel and cobalt production as battery materials for sustainable development. However, the complexity of laterite deposits and the need to control CO2 emissions challenge the enhanced global supply from laterites. This work investigates the effects of calcination as a pre-treatment for selective battery metal extraction from both limonite laterite and saprolite laterite together with concurrent achievement of CO2 mineralization. Calcination under a reducing atmosphere of CO-N2 or CO-CO2 gas mixtures can significantly enhance the extraction of critical metals from both limonite and saprolite laterites. With calcination, the hydrated silicate minerals and ferric oxides converted to reactive olivine and ferrous oxide. The calcines thus can participate in the CO2 mineralization process to stabilize CO2 as mineral carbonates and release nickel and cobalt arising from the CO2 mineral carbonation into solution as complex ions with a ligand (such as sodium nitrilotriacetate, NTA). The optimum calcination conditions are 20 ∼ 30 % CO in CO-CO2 gas mixture at 700 °C. Beyond the optimum range results in the inadequate conversion of ferric to ferrous at too low CO concentration or over calcination of ferric to metallic iron at too high CO concentration. At the optimum conditions, the nickel & cobalt extraction and CO2 mineralization can reach 90 %, 93 %, and 39 % from laterite. Each tonne saprolite with the pre-treatment of calcination can recover 20.5 kg nickel, 0.59 kg cobalt, and simultaneously sequester 142 kg CO2 as stable mineral carbonates. The pre-treatment through slightly reductive calcination enables the robust suitability of the developed process for all layers of laterites for both critical battery metal recovery and carbon mineralization.

Chasing high and stable wheat grain mineral content: Mining diverse spring genotypes under induced drought stress.

Climate change-induced drought has an effect on the nutritional quality of wheat. Here, the impact of drought at different plant stages on mineral content in mature wheat was evaluated in 30 spring-wheat lines of diverse backgrounds (modern, old and wheat-rye-introgressions). Genotypes with rye chromosome 3R introgression showed a high accumulation of several important minerals, including Zn and Fe, and these also showed stability across drought conditions. High Se content was found in genotypes with chromosome 1R. Old cultivars (K, Mg, Na, P and S) and 2R introgression lines (Fe, Ca, Mn, Mg and Na) demonstrated high mineral yield at early and late drought, respectively. Based on the low nutritional value often reported for modern wheat and negative climate effects on the stability of mineral content and yield, genes conferring high Zn/Fe, Se, and stable mineral yield under drought at various plant stages should be explicitly explored among 3R, 1R, old and 2R genotypes, respectively.

The provenance of a turbidite system within a tectonically active wrench basin: Insights from heavy mineral characteristics of Miocene sandstones in the Tabernas Basin, south‐east Spain

AbstractThis paper provides insight into the provenance of the Late Miocene turbidite succession of the Tabernas Basin. Although this area has been extensively studied, only limited attention has been paid to sediment provenance. Through heavy mineral analysis, it has been possible to identify provenance‐related signatures from the adjacent Sierra de los Filabres and Sierra Alhamilla uplifts. Stable mineral ratio data confirm that the Sierra de los Filabres provided sediment with generally higher chloritoid:tourmaline and higher Type Bii garnet abundances than those derived from the Sierra Alhamilla. By comparison, modern sediments derived from the Sierra Alhamilla have garnet compositions with larger proportions of Types A and C, suggesting that the basinal sediments were not sourced from the incipient Sierra Alhamilla Uplift. Heavy mineral analysis confirms that the Sierra de los Filabres was the primary source for the Tabernas succession, with minor variations indicating that the erosive part of the system migrated across the uplift. Input was predominantly from the Nevado–Filábride Complex, with minor amounts from the small remnant of the Alpujarride Complex attached to the southern margin of the Sierra de los Filabres. Evidence strongly suggests a single sediment routing system but identifies some subtle provenance variations. In particular, there was a shift in detrital garnet composition between the Sartenella Formation and the Verdelecho Formation, Solitary Channel and El Gordo Megabed, which is attributed here to a shift in catchment within the Sierra de los Filabres. This shift appears to have occurred during the deposition of the Sartenella Formation, since the garnet compositions of the Verdelecho Formation and Solitary Channel are similar to each other and differ from the preceding part of the Sartenella Formation. The Solitary Channel displays marked heterogeneities in provenance character, manifested by changes in chloritoid abundance, consistent with previous studies that suggest the depositional architecture in the channel was influenced by high‐frequency changes in sediment flux and sea level.

Supergene mineral assemblage from sediments affected by contact and hydrothermal metamorphism, locality Dobrá – Staré Město near Frýdek-Místek (Czech Republic)

At locality Dobrá – Staré Město, series of outcrops occur on both banks of the Morávka River. The river cuts through the sediments on the tectonic contact between the Silesian and Subsilesian units of the Outer Western Carpathians. Clayey facies of the Hradiště Formation (Early Cretaceous, Valanginian to Aptian) contains numerous tectonic fragments reaching hundreds meters in size of strongly altered (carbonatized, smectitized) subaquatic volcanic rocks of the Teschenite Association. These volcanic rocks are dominated by fine-grained to aphanitic rocks, possibly of both effusive and intrusive origin. The host sediments affected by the contact metamorphism (contact adinole) also occur. Framboidal pyrite is abundant in majority of sediments of the studied area, giving rise to efflorescences of gypsum, baryte, celestine, and a mineral of alunite group (Figure 1). A more varied assemblage of supergene minerals was recognized on a small rock outcrop at GPS coordinates N 49° 39.992’ E 018° 23.810’ (Figure 2), where it developed relatively recently after the big floods in 2010 that washed away the previous mineralization. During the first years, only gypsum crusts were detectable, while in 2023, we recognized 4 macroscopic and 5 microscopic minerals forming thin botryoidal crusts. These crusts show faint zoning, with gooey, gel-like X-ray amorphous material in the humid upper part , middle zone with abundant fibroferrite and the lower part dominated by gypsum. Gypsum forms well-developed, but frequently corroded crystals with various habitus (Figure 4A, B). Fibroferrite is present as fibrous aggregates with individual crystals of up to ca. 100–150 µm long and <1 µm thick (Figure 4C). It forms directly from the gel-like substance (Figure 4D). Rhombohedral crystals and rossete aggregates of hydroniumjarosite vary from 2 µm to 5 µm in size (Figure 4E), but the most common are dust-like coatings on rock fissures with particle size <1 µm. Rusty coatings of schwertmannite (Figure 4F), in some places accompanied by gypsum, with Fe/S at. % ratios near 4–5 are common. In some cases, the Al/Fe at. % ratio exceed 1, which might indicate presence of yet undescribed Al-analogue of schwertmannite, ill-defined alumogel, or an amorphous precursor of aluminite. Presence of ferrihydrite is possible but not confirmed. The above-mentioned Fe-rich phases are frequently accompanied by diplobacilli-shaped bacteria (Figure 4F). Slavíkite, pickeringite-halotrichite, alunogen, copiapite group mineral, hexahydrite, and melanterite (Figure 5) were also recognized by EDS and PXRD. Slavíkite and copiapite group minerals seem to be alteration products of fibroferrite. Unit-cell parameters refined from the X-ray powder diffraction are presented for all recognized phases (Table 1). Surprisingly, secondary sulfates are present on the metasediments with abundant calcite (Figure 3), which should serve as a neutralization buffer. The reason is the restricted amount of calcite available on the rock fissure surfaces, and water infiltration partially blocked by newly-formed gypsum. The albite in contact adinole (Figure 3) is unaffected by the acid rock drainage, since Na ions are not present in significant quantities in supergene phases. Since there is still enough available unaltered pyrite, we expect a shift towards more stable mineral assemblage in future. The limited amount of secondary sulfates does not present any significant harm to the environment.

Integration of Modified Solvay Process for Sodium Bicarbonate Synthesis from Saline Brines with Steelmaking for Utilization of Electric Arc Furnace Slag in CO2 Sequestration and Reagent Regeneration

In the pursuit of sustainable solutions for carbon dioxide CO2 sequestration and emission reduction in the steel industry, this study presents an innovative integration of steelmaking slag with the modified Solvay process for sodium bicarbonate (NaHCO3) synthesis from saline brines. Utilizing diverse minerals, including electric arc furnace (EAF) slag, olivine, and kimberlite, the study explored their reactivity under varied pH conditions and examined their potential in ammonium regeneration. SEM and WDXRF analyses were utilized to acquire morphological and chemical compositions of the minerals. Advanced techniques such as XRD and ICP-OES were employed to meticulously analyze mineralogical transformations and elemental concentrations. The findings demonstrate that steelmaking slag, owing to its superior reactivity and pH buffering capabilities, outperforms natural minerals. The integration of finer slag particles significantly elevated pH levels, facilitating efficient ammonium regeneration. Geochemical modeling provided valuable insights into mineral stability and reactivity, which aligned with the ICP-OES results. This synergistic approach not only aids in CO2 capture through mineral carbonation but also minimizes waste, showcasing its potential as a sustainable and environmentally responsible solution for CO2 mitigation in the steel industry.

Lithium activation pretreatment mechanism and leaching process from coal fly ash

As a result of the coal combustion process, high lithium enrichment in fly ash has been observed in some areas of China, which is considered to be a potential unconventional lithium resource. At present, most of the studies on lithium in fly ash focus on the leaching process, while there are fewer studies on the activation mechanism of roasting. In view of the above problems, the roasting activation mechanism of fly ash in the Pingshuo mining area (northern China) is investigated, and the leaching process of lithium is optimized. The activation pretreatment that destroys an inert composition of fly ash is necessary. In this study, fly ash and a mixed roasting agent (Na2CO3 and K2CO3 mass ratio of 3:1) were mixed at a mass ratio of 2:1 under 950 °C for 2 h. The results showed that the leaching rate of lithium increased by 70%. Direct acid leaching experiments show that 90% lithium in fly ash is related to insoluble aluminosilicate minerals. The mineralogical analysis of the calcined product shows that the stable aluminosilicate minerals in fly ash disappear and form nepheline KNa3(AlSiO4)3 which is soluble in acid, and the percentage of nepheline in the roasted product controls the leaching rate of lithium. The kinetic analysis of the acid leaching process of the roasting product shows that the lithium leaching process is mainly controlled by chemical reactions. Under the optimal leaching conditions, the leaching rate of lithium is 87.41%.

Impact of chlorite dehydration on intermediate-depth earthquakes in subducting slabs

Intermediate-depth earthquakes are common in the double seismic structures of many subduction zones under high pressures (~1–4 GPa). Serpentine dehydration exhibits well-established links with double seismic zone earthquakes. Additionally, dehydration of several hydrous minerals including lawsonite and chlorite underlying the upper and lower layers, respectively, may be responsible for intermediate-depth earthquakes. Here, we present experimental evidence suggesting that chlorite dehydration can trigger intermediate-depth earthquakes at the lower plane (~700 °C). We conducted deformation experiments on chlorite peridotite under high-pressure (0.5–2.5 GPa) and high-temperature (500–750 °C) using a modified Griggs apparatus. Experiments revealed the presence of faults in samples that had undergone partial chlorite dehydration with the presence of the dehydration product Ca-amphibole along these faults. Our findings confirm, together with correlation studies between seismicity and mineral stability, that a part of intermediate-depth seismicity in the lower plane of double seismic zones can be attributed to chlorite dehydration.

REACTIVE FLOW IN CARBONATE ROCKS FROM LACUSTRINE ENVIRONMENTS: THE EFFECTS OF PRESSURE AND FLUID SALINITY

The high production of CO2 from Brazilian pre-salt reservoirs requires research on CO2 interactions with carbonate reservoirs for enhanced oil recovery (EOR) or CO2 trapping. This interaction causes reactive phenomena that are not fully understood. Experimental tests on carbonate facies are crucial for understanding reactions and their impact on reservoir characteristics. This study investigates experimentally reactions generated by reactive fluid flow in carbonate rocks from two geological scenarios by analyzing chemical and morphological parameters before and after the tests. Salinity was the most significant parameter for reactive flow, impacting porosity for modern continental carbonate samples from Patagonia. However, the sample from the Brazilian pre-salt showed higher mineral stability and less mineral dissolution. Results provide data for simulating reactive transport in these rocks for CCS and understanding diagenetic processes' impact on reservoir quality.

Impact of a phosphate compound on plant metal uptake when low molecular weight organic acids are present in artificially contaminated soils

A phosphate compound can stabilize cadmium (Cd), lead (Pb), and zinc (Zn)-contaminated soils, although its effectiveness in reducing metal availability and plant uptake when low molecular weight organic acids (LMWOAs) are present is uncertain but nonetheless worth evaluating. Here, 3 % NaH2PO4 (a P compound), tartaric acid (TA), oxalic acid (OA), and mixtures of P and TA/OA are used to evaluate Indian spinach (Basella Alba L.) for soil Cd, Pb, and Zn availability and absorption. Additionally, soil metal immobilization options were examined. Of these treatments, P plus low TA (P-TA2), followed by P, decreased shoot Cd, Pb, and Zn the most, with values of 1.03, 2.52, and 104.50 mg kg−1, respectively, somewhat greater than threshold values of WHO, particularly for Pb and Zn. After harvest, P-TA2 contained >2.44, >321.70, and >290.22 mg kg−1 of total oxidizable and residual Cd, Pb, and Zn, showing that 48 %, 80 %, and 58 % of soil metals were immobilized and not taken up by the plant. P-TA2′s zeta potential, followed by P, became steadily more negative as pH increased, confirming that electrostatic adsorption was the main metal immobilization process, notably in P-TA2. However, in XRD studies, P alone generated Cd phosphate, pyromorphite, and hopeite, showing that sorption and precipitation were the predominant metal immobilization mechanisms. Finally, P-TA2 is the best in immobilizing and inhibiting metals in contaminated soils for plant absorption. Since rhizotropic LMWOAs may impact Cd, Pb, and Zn mineral stability, they should be addressed when treating Cd, Pb, and Zn-contaminated soils with P for plant growth studies.

МИНЕРАЛЬНЫЙ СОСТАВ КАК МАРКЕР ТЕРРИТОРИАЛЬНОЙ ПРИНАДЛЕЖНОСТИ ВИН ЗАЩИЩЕННЫХ НАИМЕНОВАНИЙ МЕСТ ПРОИСХОЖДЕНИЯ

The paper discusses methods for identifying wines based on regional characteristics, which consists of establishing a connection between the component composition of wines and soils corresponding to the area where grapes grow. It has been shown that markers of regional affiliation can be components whose content in wines practically does not change during the production process. The results of a study of the mineral composition of wines produced by the winemaking enterprise OOO “Imenie Sikory” are presented. Using atomic absorption spectroscopy using the Kvant Z spectrometer (NPF OOO “KORTEK”, Russia), 12 metal elements (Co, Mn, Rb, Cr, Cs, Al, Ba, Zn, Sr, Li, Na, Mg) were determined in the course of studies on atomic emission and absorption spectra. A study was also conducted of the mineral composition of soil samples from vineyards where grapes used for wine production grew. Using the methods of correlation and cluster analysis, as well as using the “random forest” algorithm (for wine samples, the initial data were the content of elements and their pairwise ratios), it was revealed that the mineral composition can serve as a marker of the regional affiliation of wine products, since the studied wine samples are within each variety have a stable mineral composition, regardless of the year of harvest (correlations between the year and the content of elements are insignificant), determined by the characteristics of the site where the grapes grow. Quantitative determination of the components of the mineral complex in combination with mathematical processing of the results allows us to establish the origin of the wines with a reasonable degree of probability. The mineral composition of the studied wines is unique and is determined by the soil characteristics of the vineyard areas of the “Semigorye” geographical object.

Lenaite (AgFeS2): A dynamically stable mineral with excellent thermoelectric performance

Diamond-like chalcopyrites have gained superior attention in thermoelectrics due to their attractive thermal transportation. On the mark of exploring environmental-friendly thermoelectric (TE) materials, this work unveils the suitability of lenaite (AgFeS2) through first-principles calculations. Owing to the beneficial band features leading to favourable effective mass, AgFeS2 exhibits good electron transport characteristics. Concurrently, the ultra-low lattice thermal conductivity of 0.47 W m−1 K−1 is realized at 500 K; ascribed to the large Grüneisen parameter, moderate phonon velocity, and Debye temperature. The combinations of these transport properties yield significant figure of merit of 0.87 at 500 K for 1.39 × 1020 holes per cm3. This study not only emphasis the TE properties of lenaite but also facilitates to understand its fundamental properties, including structural, electron and phonon-related properties.

Investigation on physico-mechanical properties and microstructural evolution patterns of heated granite after liquid nitrogen cooling

Liquid nitrogen (LN2) fracturing is recognized as an innovative reservoir enhancement technique, demonstrating significant potential in establishing high permeability pathways in geothermal development. Understanding the physico-mechanical properties and microscopic mechanisms of hot dry rock post LN2 cooling treatment is pivotal for promoting the effective deployment of LN2 fracturing. This study undertook physical and mechanical testing on a quintessential hot dry rock type-granite-post various temperature and LN2 cooling treatments. Subsequently, a multi-scale investigation was conducted on the thermal fracture-pore structure's morphological features and the evolution of mineral components. The experimental findings indicated that LN2 cooling exerts a pronounced impact on the physico-mechanical properties of high-temperature granite. Temperature-induced damage to granite can be delineated into three phases: initial phase up to 200 °C where its effects are relatively imperceptible; an intermediate phase from 200 to 500 °C characterized by gradual deterioration; and a pronounced degradation phase evident at 600 °C. Correlations between the changes in the micro pore-fracture structure of granite and its physico-mechanical property degradation were subsequently established. As temperature escalated, the area of micro-defects in the CT-reconstructed spatial distribution increased progressively. The volumetric porosity damage ratio and fractal dimensions were quantitatively introduced to characterize the fractal geometric features and distribution patterns of internal thermal fractures in granite post thermal shock. Concurrently, NMR experiments indicated that with the escalation of temperature, micropore develop and interlink to form mesopore and macropore, enhancing rock porosity connectivity. These macropores significantly influence granite's physico-mechanical and permeability characteristics. A mineral stability analysis revealed that various minerals undergo physico-chemical reactions, such as dehydration, phase transitions, decomposition, and chemical bond fractures at elevated temperatures, altering mineralogical composition and mineral strength, thus impacting the rock's macroscopic properties. Ultimately, the study delved into the damage mechanisms of granite's physico-mechanical properties from both heating and cooling perspectives during various temperature phases. The insights garnered from this investigation offer novel value in comprehending the thermal damage characteristics induced by LN2 cooling.

Trace element partitioning in basaltic systems as a function of oxygen fugacity

Along with temperature, pressure and melt chemistry, magmatic oxygen fugacity (fO2) has an important influence on liquid and solid differentiation trends and melt structure. To explore the effect of redox conditions on mineral stability and mineral-melt partitioning in basaltic systems we performed equilibrium, one-atmosphere experiments on a picrite at 1200–1110 °C with fO2 ranging from NNO-4 log units to air. Clinopyroxene crystallizes from 1180 °C to near-solidus, along with plagioclase, olivine and spinel. Olivine Mg# increases with increasing fO2, eventually reacting to pigeonite. Spinel is absent under strongly reducing conditions. Mineral-melt partition coefficients (D) of redox-sensitive elements (Cr, Eu, V, Fe) vary systematically with fO2 and, in some cases, temperature (e.g. DCr in clinopyroxene). Clinopyroxene sector zoning is common; sectors along a- and b-axes have higher AlIV, AlVI, Cr and Ti and lower Mg than c-axis sectors. In terms of coupled substitutions, clinopyroxene CaTs (MgSi = AlVIAlIV) prevails under oxidized conditions (≥ NNO), where Fe3+ balances the charge, but is limited under reduced conditions. Overall, AlIV is maximised under high temperature, oxidizing conditions and in slowly grown (a–b) sectors. High AlIV facilitates incorporation of REE (REEAlIV = CaSi), but DREE (except DEu) show no systematic dependence on fO2 across the experimental suite. In sector zoned clinopyroxenes enrichment in REE3+ in Al-rich sectors is quantitatively consistent with the greater availability of suitably-charged M2 lattice sites and the electrostatic energy penalty required to insert REE3+ onto unsuitably-charged M2 sites. By combining our experimental results with published data, we explore the potential for trace element oxybarometry. We show that olivine-melt DV, clinopyroxene-melt DV/DSc and plagioclase-melt DEu/DSr all have potential as oxybarometers and we present expressions for these as a function of fO2 relative to NNO. The crystal chemical sensitivity of heterovalent cation incorporation into clinopyroxene and the melt compositional sensitivity of the Eu2+–Eu3+ redox potential limit the use of clinopyroxene-melt and plagioclase-melt, however, olivine-melt DV affords considerable precision and accuracy as an oxybarometer that is independent of temperature, and crystal and melt composition. Variation of DV and DV/DSc with fO2 for olivine and clinopyroxene contains information on redox speciation of V in coexisting melt. By comparing the redox speciation constraints from partitioning to data from Fe-free synthetic systems and XANES spectroscopy of quenched glasses, we show that homogenous equilibria involving Fe and V species modify V speciation on quench, leading to a net overall reduction in the average vanadium valence. Mineral-melt partitioning of polyvalent species can be a useful probe of redox speciation in Fe-bearing systems that is unaffected by quench effects.